Alkane-soluble non-metallocene precatalysts

ABSTRACT

A compound of formula (1) as drawn herein, wherein M is a Group 4 metal and each R independently is a silicon-free organic solubilizing group. A method of synthesizing the compound (1). A solution of compound (1) in alkane solvent. A catalyst system comprising or made from compound (1) and an activator. A method of polymerizing an olefin monomer with the catalyst system.

FIELD

Organometallic compounds, catalysts, synthesis, and olefinpolymerization.

Publications and patents in or about the field include US20050182210A1;U.S. Pat. Nos. 5,318,935; 5,506,184; 5,889,128; 6,255,419B1;6,274,684B1; 6,534,604B2; 6,841,631B2; 6,894,128B2; 6,967,184B2;7,163,991B2; 7,196,032B2; 7,276,566B2; 7,479,529B2; 7,566,677B2;7,718,566B2; 7,754,840B2; 7,973,112B2; and 9,902,790B2. U.S. Pat. No.6,967,184B2 mentions synthesis of HN5Zr(NMe₂)₂. U.S. Pat. No.7,973,112B2 mentions a spray-dried catalyst containingbis(phenylmethyl)[N′-(2,3,4,5,6-pentamethylphenyl)-N-[2-(2,3,4,5,6-pentamethylphenyl)amino-κN]ethyl]-1,2-ethane-diaminato(2-)κN,κN′]zirconiumor “HN5Zr”, abbreviated herein as “HN5Zr dibenzyl” and(n-propylcyclopentadienyl) (tetramethylcyclopentadienyl)zirconiumdichloride.

INTRODUCTION

We describe solutions to one or more problems relating to transitioncomplexity and stability of a catalyst system that comprises, or is madefrom, a metallocene (MCN) precatalyst, a non-metallocene precatalystthat is insoluble in alkanes (“insoluble non-MCN precatalyst”), at leastone activator, and a support material (solid). The insoluble non-MCNprecatalyst (e.g., HN5Zr dibenzyl) makes a higher molecular weight (HMW)polyethylene component of a bimodal polyethylene composition. The MCNprecatalyst is soluble in alkanes and makes a lower molecular weight(LMW) polyethylene component of the bimodal polyethylene composition.The catalyst system is formulated in two parts. A first part comprises aslurry of the support, an alkanes solvent, the at least one activator,all of the insoluble non-MCN precatalyst (e.g., HN5Zr dibenzyl), andsome of the MCN precatalyst. A second part comprises a solution of theremainder of the MCN precatalyst in an alkane(s) solvent, but none ofthe insoluble non-MCN precatalyst, activator, or support.

In a “combining-the-parts” feed method, the first and second parts arefed separately into an in-line mixer, where they mix to make thecatalyst system. This fresh catalyst system is fed into a singlepolymerization reactor. The combining-the-parts feed method has someflexibility to achieve various polymerization rates and to enable makingvarious bimodal polyethylene compositions with various polymerattributes in the single polymerization reactor. For example, the flowrate of the feed of the second part may be adjusted to supplement theeffect of the portion of the MCN precatalyst in the first part (e.g.,make more of the LMW polyethylene component), or to “trim” or modulatethe effects of the insoluble non-MCN precatalyst (e.g., HN5Zr dibenzyl)of the first part (e.g., increase the LMW/HMW ratio), enabling makingvarious bimodal polyethylene compositions. Thus, the second part iscalled a “trim catalyst”. The combining-the-parts feed method allowscontrol within limits of the polymerization reaction making the bimodalpolyethylene composition and varying within limits of the LMW/HMW ratioso as to transition between various bimodal polyethylene compositions inthe single polymerization reactor.

The first part beneficially contains all of the insoluble non-MCNprecatalyst, activator, and some of the MCN precatalyst, and ispre-mixed with a desired amount of the second part (trim catalyst) tomake a bimodal catalyst system before it enters a polymerizationreactor. This is done in order to make a so-called reactor blend of theHMW and LMW polyethylene components in the polymerization reactor,whereby the HMW and LMW polyethylene components are made in situ inintimate contact with each other. This reactor blend results in abimodal polyethylene composition having better mixing of the HMW and LMWpolyethylene components, and thus a decreased gel content. If theinsoluble non-MCN precatalyst and activator and the MCN precatalyst andactivator would be fed separately into the polymerization reactor, theresulting HMW and LMW polyethylene components would be initially madeseparately in the reactor, and may not homogeneously mix togetherthereafter. This may make a comparative bimodal polyethylene compositionundesirably having increased gel content, where portions of the HMWpolyethylene component may make gels. The comparative bimodalpolyethylene composition may have a gel content that is too high forapplications requiring clarity such as films and/or for applicationsrequiring high strength such as pipes.

Unfortunately the HMW/LMW ratio in the combining-the-parts feed methodcannot be zero or near zero because the first part of the catalystsystem contains both the MCN precatalyst and the insoluble non-MCNprecatalyst (e.g., HN5Zr dibenzyl), and therefore the bimodalpolyethylene composition made thereby always contains some amount ofboth the LMW polyethylene component and the HMW polyethylene component.

Further, transitions between insoluble non-MCN precatalyst (e.g., HN5Zrdibenzyl) and a different precatalyst or between different amounts ofinsoluble non-MCN precatalyst (“catalyst transitions”) in the singlepolymerization reactor are complex. For example, it is complex totransition from a first catalyst system (abbreviated LMW-CAT-1,insoluble non-MCN precatalyst) to a second catalyst system (abbreviatedLMW-CAT-2, insoluble non-MCN precatalyst), wherein LMW-CAT-1 andLMW-CAT-2 are different from each other and from insoluble non-MCNprecatalyst. Even though the insoluble non-MCN precatalyst is the samein the first parts of both the first and second catalyst systems, boththe first and second parts of the first catalyst system must be replacedfor the transition because both the first and second parts contain theno longer wanted LMW-CAT-1 component.

Also, certain insoluble non-MCN precatalyst (e.g., HN5Zr dibenzyl)become unstable after being mixed with the activator. It is necessary tochill those first parts (containing unstable/insoluble non-MCNprecatalyst) of the catalyst system to about −10 degrees Celsius (° C.)for shipment or storage thereof. Then, the second part may need to bereformulated to withstand cooling “shock” when it contacts the chilledfirst part in the in-line mixer. Or the first part may need to be warmedbefore being fed into the in-line mixer.

And because insoluble non-MCN precatalyst (e.g., HN5Zr dibenzyl) isinsoluble in alkanes, it is not suitable for use in the second part(trim catalyst) in the combining-the-parts feed method.

SUMMARY

A compound of formula (1):

wherein M is a Group 4 metal and each R independently is a silicon-freeorganic solubilizing group.

A method of synthesizing the compound of formula (1) as described below.

A solution of compound (1) in alkane solvent.

A catalyst system comprising or made from compound (1) and an activator.

A method of polymerizing an olefin monomer with the catalyst system.

The compound (1) may be contacted with an activator to make a catalyst,which is useful for polymerizing one or more olefin monomers to make acorresponding polyolefin.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a prophetic Gel Permeation Chromatogram (GPC) of a propheticbimodal polyethylene composition made according to the prophetic methodof Example 9.

DETAILED DESCRIPTION

The Summary, Claims, and Abstract are incorporated here by reference.Certain embodiments are described below as numbered aspects for easycross-referencing. Embodiments of the invention provide an alternativenon-MCN precatalyst composition, which has two silicon-free organicsolubilizing groups. The composition beneficially has a significantlyincreased solubility in alkanes and/or a significantly increasedcatalyst light-off, both compared to those of HN5Zr dibenzyl.

Aspect 1. A compound of formula (1), drawn above, wherein M is Zr or Hfand each R independently is methyl, an unsubstituted (C₂-C₄)alkyl group,an unsubstituted (C₅-C₁₂)alkyl group (e.g., an unsubstituted(C₅-C₉)alkyl group or an unsubstituted (C₁₀-C₁₂)alkyl group), anunsubstituted or substituted quaternary-arylalkyl group, or both Rgroups are bonded together to give R′-R′, wherein R′-R′ is anunsubstituted or substituted (aryl)alkylene. Each R group and R′-R′group is free of a cyclopentadienyl group, a silicon atom, acarbon-carbon double bond, and a carbon-carbon triple bond. Eachsubstituent independently may be selected from unsubstituted(C₁-C₅)alkyl, halogen, —Oalkyl, and —N(alkyl)₂.

Each quaternary-arylalkyl group sequentially contains a quaternaryalkyl, a phenylene, and a (C₁-C₃)alkylene linker. The quaternary alkylis bonded to the phenylene, which is bonded to the (C₁-C₃)alkylenelinker, which is bonded to the metal M. The (C₁-C₃)alkylene linker andR′-R′ groups are divalent. The quaternary alkyl contains a quaternarycarbon atom, which may be directly or indirectly bonded to thephenylene. A quaternary carbon atom is an element having atomic number 6in the Periodic Table of the Elements that is bonded to four othercarbon atoms.

Aspect 2. The compound of aspect 1 wherein each R independently is aquaternary-(aryl)alkyl group of formula —(C(R^(A))₂)_(m)QCR¹R²R³,wherein subscript m is 1, 2, or 3; wherein each R^(A) independently is Hor (C₁-C₃)alkyl; wherein each Q independently is absent, a(C₁-C₃)alkylene, or an unsubstituted or substituted phenylene; whereineach R¹, R², and R³ is independently H or a (C₁-C₁₅)alkyl thatindependently is unsubstituted or substituted; wherein each substitutedgroup independently has one or more substituents independently selectedfrom unsubstituted (C₁-C₅)alkyl, halogen, —Oalkyl, and —N(alkyl)₂. Insome aspects at least one, alternatively two, alternatively each of R¹,R², and R³ is independently a (C₁-C₁₅)alkyl. In some aspects, with theproviso that when subscript m is 2, the resulting (C(R^(A))₂)_(m) is notC(R^(A))₂CH(R^(A)) or C(R^(A))₂CH₂; and when subscript m is 3, theresulting (C(R^(A))₂)_(m) is not C(R^(A))₂CH(R^(A))C(R^(A))₂ orC(R^(A))₂CH₂C(R^(A))₂. The optional proviso is intended to excludecompounds that may be prone to undergoing beta-hydride elimination. Insome aspects subscript m is 2, alternatively 1. In some aspects eachR^(A) independently is H or unsubstituted (C₁-C₂)alkyl, alternatively Hor methyl, alternatively H. In some aspects each Q is absent. In someaspects at least one, alternatively each Q is present. When each Q ispresent, each Q independently may be a (C₁-C₃)alkylene, alternativelyCH₂, alternatively CH₂CH₂, alternatively CH₂CH₂CH₂, alternativelyCH₂CH(CH₃). Alternatively each Q independently may be unsubstituted1,4-phenylene, unsubstituted 1,3-phenylene, or 1,2-phenylene;alternatively unsubstituted 1,2-phenylene; alternatively unsubstituted1,3-phenylene; alternatively unsubstituted 1,4-phenylene. The1,2-phenylene is benzene-1,2-diyl; 1,3-phenylene is benzene-1,3-diyl;and 1,4-phenylene is benzene-1,4-diyl. The “unsubstituted phenylene”means the phenylene is of formula C₆H₄. In some aspects each R group isunsubstituted.

Aspect 3. The compound of aspect 1 or 2 wherein at least one,alternatively each R is independently —CH₂QCR¹R²R³; wherein each Qindependently is unsubstituted phenylene; wherein each R¹, R², and R³ isindependently an unsubstituted (C₁-C₁₅)alkyl.

Aspect 4. The compound of aspect 2 or 3 wherein at least one,alternatively each R is —CH₂-(unsubstituted phenylene)-CR¹R²R³; whereineach unsubstituted phenylene is unsubstituted 1,4-phenylene,unsubstituted 1,3-phenylene, or unsubstituted 1,2-phenylene; whereineach R¹, R², and R³ is independently unsubstituted (C₁-C₁₅)alkyl,alternatively (C₁-C₃)alkyl, alternatively methyl. In some aspects one Ris the —CH₂CR¹R²R³ and the other R is an unsubstituted (C₁-C₁₅)alkyl. Insome aspects the phenylene is (i) unsubstituted 1,4-phenylene; (ii)unsubstituted 1,3-phenylene; or (iii) unsubstituted 1,2-phenylene. Insome aspects the phenylene is unsubstituted 1,4-phenylene.

Aspect 5. The compound of aspect 1 wherein each R independently ismethyl, an unsubstituted (C₂-C₄)alkyl group, or an unsubstituted(C₅-C₁₂)alkyl group (e.g., an unsubstituted (C₅-C₉)alkyl group). In someaspects each R is methyl, alternatively each R is an unsubstituted(C₂-C₄)alkyl group, alternatively each R is an unsubstituted(C₅-C₉)alkyl group, alternatively one R is methyl and the other R is anunsubstituted (C₅-C₉)alkyl group. In some aspects the unsubstituted(C₅-C₉)alkyl group is 2,2-dimethylpropyl (neopentyl).

Aspect 6. The compound of aspect 1 wherein both R groups are bondedtogether to give R′-R′, wherein R′-R′ is an unsubstituted or substitutedalkylene, alternatively a substituted (C₄-C₅)alkylene. In some aspectsR′-R′ is —(CH₂)₃C(H)(R⁴)CH₂— or —CH₂ (C(R⁴)))₂CH₂—, wherein each R⁴independently is an unsubstituted (C₁-C₅)alkyl. The R′-R′ may be2,2,3,3-tetramethylbutane-1,4-diyl or2-(2′,2′-dimethylpropyl)-pentane-1,5-diyl.

Aspect 7. The compound of aspect 1 wherein both R groups are bondedtogether to give R′-R′, wherein R′-R′ is a substituted arylalkylene,alternatively a 4-(unsubstituted (C₁-C₅)alkyl)-1,2-bezenedimethylene.The 4-(unsubstituted (C₁-C₅)alkyl)-1,2-bezenedimethylene is—CH₂-[4-(unsubstituted (C₁-C₅)alkyl-(1,2-phenylene)]-CH₂—. In someaspects the 4-(unsubstituted (C₁-C₅)alkyl)-1,2-bezenedimethylene is4-(2,2-dimethylpropyl)-1,2-benzenedimethylene (i.e.,—CH₂-[4-(CH₃C(CH₃)₂CH₂)-(1,2-phenylene)]-CH₂—).

Aspect 8. The compound of any one of aspects 1 to 7 wherein M is Zr. Inother aspects M is Hf.

Aspect 9. The compound of any one of aspects 1 to 8 characterized bysolubility in hexanes containing at least 60 weight percent n-hexane(CH₃(CH₂)₄CH₃) of at least 0.10 weight percent based on total weight ofthe compound and hexanes.

Aspect 10. A compound of formula (1A), (1B), (1C), or (1D):

Aspect 11. A method of synthesizing the compound of formula (1) of anyone of aspects 1 to 10, the method comprising contacting a compound offormula (2)

wherein M is as defined for compound (1) and each X independently is C₁,Br, or I, with an organometallic reagent of formula X¹MgR or M¹R_(n);wherein R is as defined for compound (1) according to any one of aspects1 to 10; X¹ is Cl, Br, or I; M¹ is selected from Li, Zn, Sn, and Cu; andsubscript n is an integer from 1 to 4 and is equal to the formaloxidation state of M¹; in an aprotic solvent under effective reactionconditions, thereby synthesizing the compound of formula (1). In someaspects the organometallic reagent X¹MgR is used and isX¹MgC((R^(A))₂)_(m)QCR¹R²R³, alternatively X¹MgCH₂QCR¹R²R³,alternatively X¹MgCH₂C(CH₃)₃, alternatively 2,2-dimethylpropylmagnesiumchloride or 4-tert-butylbenzylmagnesium chloride; wherein X¹ is Cl orBr, alternatively Cl, alternatively Br. In some aspects theorganometallic reagent M¹R_(n) is used and isM¹(C((R^(A))₂)_(m)QCR¹R²R³)_(n), alternatively M¹(CH₂QCR¹R²R³)_(n),alternatively M¹(CH₂QC(CH₃)₃)_(n), alternatively 2,2-dimethylpropyllithium or 4-tert-butylbenzyl lithium; wherein M¹ is Li. In some aspectsthe molar ratio of moles of compound (2) to moles of the organometallichalide reagent is from 1:2 to 1:10.

Aspect 12. The method of aspect 11 further comprising a preliminary stepof contacting a compound of formula (3):

wherein each R¹⁰ independently is (C₁-C₁₅)alkyl, alternatively(C₁-C₆)alkyl, with a reagent of formula X—C(CH₃)₃, wherein X is asdefined for the compound (2), in an aprotic solvent under effectivereaction conditions to synthesize the compound (2). In some aspectsreagent X—C(CH₃)₃ is tert-butyl chloride, tert-butyl bromide ortert-butyl iodide; alternatively tert-butyl chloride (also known as1-chloro-2,2-dimethylpropane).

Aspect 13. The method of aspect 12, further comprising a preliminarystep of contacting a compound of formula (4):

with a reagent of formula M(N(R¹⁰)₂)₄, wherein M is as defined forcompound (1) and each R¹⁰ independently is (C₁-C₁₅)alkyl, in an aproticsolvent under effective reaction conditions to synthesize the compound(3). In some aspects each R¹⁰ independently is alternatively(C₁-C₆)alkyl, alternatively methyl or ethyl, alternatively methyl. Insome aspects the compound being synthesized in aspects 11 to 13 is thecompound of any one of aspects 1 to 10. The molar ratio of compound (4)to M(N(R¹⁰)₂)₄ may be from 1:10 to 10:1, alternatively from 1:5 to 5:1,alternatively from 1:2 to 2:1, alternatively 1:1.

In the Examples described later, compounds (1A) to (1C) were synthesizedaccording to the method of aspect 11. Compound (1 D) was synthesizeddirectly from compound (4).

Aspect 14. A solution of the compound of any one of aspects 1 to 10 inan alkane, wherein the solution is a liquid at 25 degrees Celsius and101 kilopascals and the concentration of the compound in the solution isat least 0.10 weight percent based on weight of the solution. The alkanemay be hexanes, isopentane, a mineral oil, or a combination of any twoor more thereof. The alkane may be hexanes and/or isopentane,alternatively hexanes and/or a mineral oil, alternatively isopentaneand/or a mineral oil.

Aspect 15. A catalyst system comprising, or made from, a compound of anyone of aspects 1 to 10, an activator, optionally a hydrocarbon solvent,and optionally a support material. The catalyst system may be ahomogeneous catalyst system (one phase) or a heterogeneous catalystsystem (two phase). The activator may be an alkylaluminoxane or atrialkylaluminum compound. In some aspects the catalyst system comprisesthe support material, and the support material is an untreated silica,alternatively a calcined untreated silica, alternatively a hydrophobingagent-treated silica, alternatively a calcined and hydrophobingagent-treated silica. In some aspects the hydrophobing agent isdichlorodimethylsilane. The catalyst system is useful as an olefinpolymerization catalyst system in solution phase, slurry phase, and gasphase polymerization reactions, such as may be used for makingpolyethylene polymers or polypropylene polymers. In some aspects theformulation is free of Cr, Ti, Mg, or an unsubstituted or substitutedcyclopentadienyl group; alternatively Cr, Ti, and Mg; alternatively anunsubstituted or substituted cyclopentadienyl group.

Aspect 16. The catalyst system of aspect 15 further comprising ametallocene precatalyst, or a product of an activation reaction of themetallocene precatalyst and an activator. Examples of such metalloceneprecatalysts are described later. The activator contacting themetallocene precatalyst may be the same as, alternatively different thanthe activator contacting the compound (1). In some aspects themetallocene precatalyst or product of activation thereof furthercomprises a support material, which may be the same as or different thanthe optional support material for compound (1).

Aspect 17. A method of making a polyolefin polymer, the methodcomprising contacting the catalyst system of aspect 15 or 16 with atleast one olefin monomer selected from ethylene, propylene, a(C₄-C₂₀)alpha-olefin, and 1,3-butadiene in a polymerization reactorunder effective polymerization conditions, thereby making the polyolefinpolymer. In some aspects the at least one olefin monomer is ethylene andoptionally a (C₄, C₆, or C₈)alpha-olefin. The polymerization reactor maybe a reactor configured for solution phase polymerization, slurry phasepolymerization, or gas phase polymerization of the at least one olefinmonomer. The reactors and effective polymerization conditions forsolution phase polymerization, slurry phase polymerization, or gas phasepolymerization are well known.

Without wishing to be bound by theory, it is believed that thequaternary-hydrocarbyl groups, R, impart enhanced solubility of compound(1) in alkanes. The enhanced solubility may be characterized forcomparison purposes as solubility of compound (1) in hexanes containingat least 60 weight percent n-hexane (CH₃(CH₂)₄CH₃) as measured using theSolubility Test Method, described below. Advantageously, compound (1)has a solubility in hexanes containing at least 60 weight percentn-hexane of at least 0.10 wt % in an alkane solvent. In some aspects,the solubility of compound (1) in hexanes containing at least 60 weightpercent n-hexane is from 0.10 to 25 wt %, alternatively from 0.5 wt % to25 wt %, alternatively from 1 wt % to 25 wt %, alternatively from 2 wt %to 25 wt %, alternatively from 3 wt % to 25 wt %, alternatively from 5wt % to 25 wt %, alternatively from 10.0 wt % to 25 wt %, alternativelyfrom 15 wt % to 25 wt %, alternatively from 20.0 wt % to 25 wt %,alternatively from 0.10 to 20.0 wt %, alternatively from 0.5 wt % to20.0 wt %, alternatively from 1 wt % to 15 wt %, alternatively from 2 wt% to 15 wt %, alternatively from 3 wt % to 15 wt %, alternatively from 5wt % to 15 wt %, alternatively from 1.0 wt % to 15 wt %, alternativelyfrom 1.0 wt % to 10.0 wt %, as measured using the Solubility TestMethod. Advantageously, the solubility in hexanes containing at least 60weight percent n-hexane of compound (1) is surprisingly better than thatof HN5Zr dibenzyl, which has solubility of just 0.03 wt % in hexanescontaining at least 60 weight percent n-hexane.

Compound (1) may be employed either in a first part (a main catalyst) orin a second part (as trim catalyst) of the catalyst system. Compound (1)is useful in the combining-the-parts feed method described in theINTRODUCTION. Additionally, compound (1) may be combined with anactivator and the combination fed to an in-line mixer or apolymerization reactor independently from feeding of a combination ofthe metallocene precatalyst and activator to the same in-line mixer orpolymerization reactor. This so-called “separate-the-parts” feed methodbeneficially avoids the aforementioned transition complexity oftransitions between catalyst systems and enables greater operationalflexibility for olefin polymerization processes in a singlepolymerization reactor.

Compound (1) has sufficient solubility in alkanes such that it may beemployed as a HMW precatalyst, with or without a LMW precatalyst, in thecatalyst system. The increased solubility of compound (1) in alkanesalso enables greater flexibility in a polymerization processes run in asingle polymerization reactor and for making a bimodal polyethylenecomposition comprising LMW and HMW polyethylene components.

Compound (1) solves the instability problem of prior alkanes-insolublenon-MCN precatalysts because compound (1) may be stored as a solution inalkanes free of activator.

The catalyst system made from compound (1) and activator has fasterlight-off than a comparative catalyst system made from HN5Zr dibenzyland the same activator. And yet compound (1) may make a polyethylenehaving same MWD as MWD of a polyethylene made by the comparativecatalyst system. The faster light-off of the catalyst system made fromcompound (1) and the activator may beneficially result in reduceddistributor plate fouling in a gas phase polymerization reactorcontaining a recycle loop, whereby some polymer particles with activecatalyst are entrained back to the reactor where they can grow and foulthe distributor plate. The faster light-off of the catalyst system maybe characterized as a shorter time to maximum temperature as measured invitro using 1-octene as monomer according to the Light-off Test Method,described later.

The catalyst system made from compound (1) and activator enables makingof polyethylene resins having a lesser proportion of particlescharacterized as “fines”, which is defined later. There are manywell-known reasons why fines can cause problems in operating a gas phasepolymerization reactor having a recycle line and/or an expanded uppersection, such as UNIPOL™ reactor from Univation Technologies, LLC orother reactors. Fines are known to lead to an increased tendency forstatic and sheeting in such reactor. Fines can increase particlecarry-over from the reactor into the recycle line and result in foulinginside the recycle loop, such as in a heat exchanger, compressor, and/ordistributor plate. Fines can also build up in the reactor's expandedsection because, it is believed, fines are more prone and/or susceptibleto electrostatic forces. Fines can also cause problems with polyethylenepolymers made by gas phase polymerization in such a reactor. Fines maycontinue to polymerize in cold zones of the reactor, either in therecycle loop or expanded section, and produce a polyethylene having amolecular weight that is higher than that targeted in the bulk fluidizedbed. Fines can eventually make their way back from the recycle loop intothe fluidized bed, and then into the polyethylene product, leading tohigher level of gels in the polyethylene product. The polyethyleneresins made by the catalyst system made from compound (1) and anactivator have reduced wt % of fines.

The catalyst system made from compound (1) and activator enables makingof polyethylene resins having larger particle sizes than those ofpolyethylene resins made by the comparative catalyst system made fromthe HN5Zr dibenzyl and the same activator. The larger particle sizes ofpolyethylene resins made by the inventive catalyst system may be usefulfor decreasing settled bulk densities of the resin. Resins with a higherproportion of fines can have a higher settled bulk density because thesmaller particles of the fines can shift downward and fill in spacesbetween larger particles. If the settled bulk density is too high, theresin can be difficult to fluidize, causing localized overheating andforming resin chunks in certain regions of the reactor process such asnear edges of a distributor plate or in a product discharge system.

A polyethylene resin may be made using a bimodal catalyst system,wherein an alkanes solution of compound (1) is used as trim catalyst(second part) and a combination of all of an MCN precatalyst, activator,and a remainder of compound (1) are used as the first part, all of acombining-the-parts feed method, may have reduced gel content comparedto a polyethylene resin made using the same bimodal catalyst systemexcept wherein a supported HN5Zr dibenzyl is used as trim catalyst and aremainder of HN5Zr dibenzyl and the same MCN precatalyst are used as thefirst part. Because the compound (1) has significantly greatersolubility in hexanes containing at least 60 weight percent n-hexane,than does HN5Zr dibenzyl, compound (1) has significantly greatersolubility in alkanes solvents such as mineral oil than does HN5Zrdibenzyl. This means compound (1) may be fed as an alkanes solution(e.g., typically a solution in mineral oil) as a trim catalyst in the“combining-the-parts” feed method described earlier, whereby it can bemixed with a remainder of compound (1) and all of the MCN precatalyst ofa first part in an in-line mixer to give a bimodal catalyst system thatmay make a bimodal polyethylene composition without the increased gelcontent found for HN5Zr dibenzyl for the reasons described above, and tosolve the earlier gel problem.

Without being bound by theory, it is believed that if in a comparativeprecatalyst of formula (1) wherein the subscript m would be 0, and thusthe quaternary carbon atom of the quaternary-hydrocarbyl groups would bedirectly bonded to metal M, a synthesis of such a comparativeprecatalyst may be difficult. Alternatively, if in a comparativeprecatalyst of formula (1) wherein the subscript m would be 4 orgreater, and thus the quaternary carbon atom of thequaternary-hydrocarbyl groups would be spaced apart from the metal M byadditional carbon atoms, a steric effect of the closer inventivequaternary arylalkyl functional group on metal M could be lost.

Compound (1)

Compound (1) is a non-metallocene precatalyst of molecular formula(C₂₆H₃₉N₃)MR₂, wherein M and R groups are as defined for compound (1).Compound (1) contains two N-substituted pentamethyl-phenyl groups andmay have general chemical namebis(quaternary-hydrocarbyl)[N′-(2,3,4,5,6-pentamethylphenyl)-N-[2-(2,3,4,5,6-pentamethylphenyl)amino-κN]ethyl]-1,2-ethane-diaminato(2-)κN,κN′](zirconiumor hafnium). For example, when M is Zr and each R is4-tertiary-butylbenzyl, compound (1) may have chemical namebis(4-tert-butylbenzyl)[N′-(2,3,4,5,6-pentamethylphenyl)-N-[2-(2,3,4,5,6-pentamethylphenyl)amino-κN]ethyl]-1,2-ethane-diaminato(2-)κN,κN′]zirconium.

In compound (1) each R independently may be the unsubstituted orsubstituted quaternary-hydrocarbyl group of formula—C((R^(A))₂)_(m)QCR¹R²R³, wherein subscript m, R^(A), R1, R2, and R3 areas defined for compound (1) of any one of aspects 2 to 6. In someaspects, each R is the same or different and is independently selectedfrom: methyl; 2,2-dimethylpropyl; 2,2-dimethylhexyl; 2,2-dimethyloctyl;2-ethylhexyl; 2-ethyloctyl; 2-tert-butylphenylmethyl;3-tert-butylphenylmethyl; 4-tert-butylphenylmethyl; 2-ethylphenylmethyl;3-n-butylphenylmethyl; 4-n-butylphenylmethyl; 2-n-butylphenylmethyl;3-ethylphenylmethyl; 4-ethylphenylmethyl; 2-n-octylphenylmethyl;3-n-octylphenylmethyl; and 4-n-octylphenylmethyl. In some aspects each Ris the same.

In some aspects compound (1) is selected from: (i) compound (1A); (ii)compound (1B); (iii) compound (1) wherein each R is2-tert-butylphenylmethyl; (iv) compound (1) wherein each R is3-tert-butylphenylmethyl; (v) compound (1) wherein one R is4-tert-butylphenylmethyl and the other R is methyl; (vi) compound (1)wherein one R is 2,2-dimethylpropyl (i.e., CH₂C(CH₃)₃) and the other Ris methyl; (vii) compound (1) wherein each R is 2-ethylhexyl; (viii)compound (1) wherein each R is 2,2-dimethylpropyl I; (ix) compound (1)wherein each R is 2,2-dimethylhexyl; (x) compound (1) wherein each R ishexyl; (xi) compound (1) wherein both R groups are bonded together toform 4-(2,2-dimethylpropyl)-1,2-benzenedimethylene; (xii) compound (1)wherein both R groups are bonded together to form2-(2′,2′-dimethylpropyl)-pentane-1,5-diyl; (xiii) compound (1) whereinboth R groups are bonded together to form2,2,3,3-tetramethylbutane-1,4-diyl; and (xiv) a combination of any twoor more of (i) to (xiii) (e.g., (i) and (ii)). In some aspects compound(1) is any one of compounds (1A) to (1 D), alternatively compound (1) isselected from any three of compounds (1A) to (1 D), alternativelycompound (1) is compound (1A) or (1B), alternatively compound (1) iscompound (1C) or (1D), alternatively compound (1) is compound (1A),alternatively compound (1) is compound (1B), alternatively compound (1)is compound (1C), alternatively compound (1) is compound (1D).

Compound (1) includes solvates and solvent-free embodiments thereof.

The substituted quaternary-hydrocarbyl group is formally derived byreplacing from 1 to 4 hydrogen atoms (i.e., carbon-bonded hydrogenatoms, H—C, independently chosen) of the unsubstituted hydrocarbon witha substituent group.

In some aspects each unsubstituted quaternary-hydrocarbyl group has from4 to 50 carbon atoms, alternatively from 4 to 20 carbon atoms,alternatively from 4 to 10 carbon atoms, alternatively from 5 to 6carbon atoms.

Compound (1), after being activated with an activator, makes a catalystsystem that is effective for polymerizing one or more olefin monomers,thereby making a polyolefin polymer. Each olefin monomer isindependently selected from ethylene, propylene, a (C₄-C₂₀)alpha-olefin,and 1,3-butadiene. Each (C₄-C₂₀)alpha-olefin independently may be1-butene, 1-hexene, or 1-octene; alternatively 1-butene or 1-hexene;alternatively 1-butene; alternatively 1-hexene. In some aspects theolefin monomer is selected from ethylene, a (C₄-C₂₀)alpha-olefin, and1,3-butadiene; alternatively ethylene and a (C₄-C₂₀)alpha-olefin;alternatively ethylene and 1-hexene; alternatively ethylene and1-octene; alternatively ethylene.

Compound (1) may be used with a metallocene catalyst to make a bimodalcatalyst system for making a bimodal polyethylene composition. In someaspects, compound (1) is combined with a metallocene precatalyst orcatalyst, at least one activator, and optionally a support, to make acatalyst system comprising, or made from, the metallocene precatalyst,compound (1), the at least one activator, and optionally the support(solid, particulate material). Compound (1) is useful for making a HMWpolyethylene component of a bimodal polyethylene composition. Themetallocene precatalyst is useful for making a LMW polyethylenecomponent of the bimodal polyethylene composition. The bimodalpolyethylene composition is made by polymerizing one or more olefinmonomers. In some aspects the bimodal polyethylene composition is madefrom ethylene only; alternatively from a combination of ethylene and one(C₄-C₈)alpha-olefin comonomer. Compound (1) may also be interchangeablyreferred to as a precatalyst, a catalyst component, or a HMW catalyst.

Also contemplated is a derivative of compound (1) wherein compound (4)is covalently bonded to a carrier polymer. In an embodiment, the middlenitrogen atom (bonded to two ethylene groups) in compound (4) may bondedto the carrier polymer. Alternatively a methyl group of one of thepentamethylcyclopentadienyl groups of compound (4) might be replacedwith an alkylene group that is bonded to the carrier polymer.Ligand-bound polymers are generally described in U.S. Pat. Nos.5,473,202 and 5,770,755.

Synthesis

In the method of synthesizing compound (1), including the preliminarysteps, an aprotic solvent may be used in any one or more of thecontacting steps. The aprotic solvent independently may be a hydrocarbonsolvent such as an alkylarene (e.g., toluene, xylene), an alkane, achlorinated aromatic hydrocarbon (e.g., chlorobenzene), a chlorinatedalkane (e.g., dichloromethane), a dialkyl ether (e.g., diethyl ether),or a mixture of any two or more thereof. The aprotic solvent may be anyone of those used later in the synthesis Examples.

Each of the contacting steps in the method of synthesizing compound (1)independently may be conducted under effective reaction conditions.Effective reaction conditions may comprise techniques for manipulatingair-sensitive and/or moisture-sensitive reagents and reactants such asSchlenk-line techniques and an inert gas atmosphere (e.g., nitrogen,helium, or argon). Effective reaction conditions may also comprise asufficient reaction time, a sufficient reaction temperature, and asufficient reaction pressure. Each reaction temperature independentlymay be from −78° to 120° C., alternatively from −30° to 30° C. Eachreaction pressure independently may be from 95 to 105 kPa, alternativelyfrom 99 to 103 kPa. Progress of any particular reaction step may bemonitored by analytical methods such as nuclear magnetic resonance (NMR)spectroscopy, mass spectrometry to determine a reaction time that iseffective for maximizing yield of intended product. Alternatively, eachreaction time independently may be from 30 minutes to 48 hours.

Solvent

“Hydrocarbon solvent” means a liquid material at 25° C. that consists ofcarbon and hydrogen atoms, and optionally one or more halogen atoms, andis free of carbon-carbon double bonds and carbon-carbon triple bonds.The hydrocarbon solvent may be an alkane, an arene, or an alkylarene(i.e., arylalkane). Examples of hydrocarbon solvents are alkanes such asmineral oil, pentanes, hexanes, heptanes, octanes, nonanes, decanes,undecanes, dodecanes, etc., and toluene, and xylenes. In one embodiment,the hydrocarbon solvent is an alkane, or a mixture of alkanes, whereineach alkane independently has from 5 to 20 carbon atoms, alternativelyfrom 5 to 12 carbon atoms, alternatively from 5 to 10 carbon atoms. Eachalkane independently may be acyclic or cyclic. Each acyclic alkaneindependently may be straight chain or branched chain. The acyclicalkane may be pentane, 1-methylbutane (isopentane), hexane,1-methylpentane (isohexane), heptane, 1-methylhexane (isoheptane),octane, nonane, decane, or a mixture of any two or more thereof. Thecyclic alkane may be cyclopentane, cyclohexane, cycloheptane,cyclooctane, cyclononane, cyclodecane, methycyclopentane,methylcyclohexane, dimethylcyclopentane, or a mixture of any two or morethereof. Additional examples of suitable alkanes include Isopar-C,Isopar-E, and mineral oil such as white mineral oil. In some aspects thehydrocarbon solvent is free of mineral oil. The hydrocarbon solvent mayconsist of one or more (C₅-C₁₂)alkanes.

Catalyst System

The catalyst system comprises a combination of compound (1) and anactivator; alternatively the catalyst system comprises an activationreaction product of an activation reaction of compound (1) and theactivator.

The catalyst system may be made under effective activation conditions.Effective activation conditions may comprise techniques for manipulatingcatalysts such as in-line mixers, catalyst preparation reactors, andpolymerization reactors. The activation may be performed in an inert gasatmosphere (e.g., nitrogen, helium, or argon). Effective activationconditions may also comprise a sufficient activation time and asufficient activation temperature. Each activation temperatureindependently may be from 20° to 800° C., alternatively from 300° to650° C. Each activation time independently may be from 10 seconds to 2hours.

“Activator”, also known as a cocatalyst, is a compound or a compositioncomprising a combination of reagents, wherein the compound orcomposition increases the rate at which a transition metal compound(e.g., compound (1) or metallocene precatalyst) oligomerizes orpolymerizes unsaturated monomers, such as olefins, such as ethylene or1-octene. An activator may also affect the molecular weight, degree ofbranching, comonomer content, or other properties of the oligomer orpolymer (e.g., polyolefin). The transition metal compound (e.g.,compound (1) or metallocene precatalyst) may be activated foroligomerization and/or polymerization catalysis in any manner sufficientto allow coordination or cationic oligomerization and or polymerization.Typically, the activator contains aluminum and/or boron, alternativelyaluminum. Examples of suitable activators are alkylaluminoxanes andtrialkylaluminum compounds.

Aluminoxane (also known as alumoxane) activators may be utilized as anactivator for one or more of the precatalyst compositions includingcompound (1) or metallocene precatalyst. Aluminoxane(s) are generallyoligomeric compounds containing —Al(R)—O— subunits, where R is an alkylgroup; which are called alkylaluminoxanes (alkylaluminoxanes). Thealkylaluminoxane may be unmodified or modified. Examples ofalkylaluminoxanes include methylaluminoxane (MAO), modifiedmethylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane.Unmodified alkylaluminoxanes and modified alkylaluminoxanes are suitableas activators for precatalysts such as compound (1). Mixtures ofdifferent aluminoxanes and/or different modified aluminoxanes may alsobe used. For further descriptions, see U.S. Pat. Nos. 4,665,208;4,952,540; 5,041,584; 5,091,352; 5,206,199; 5,204,419; 4,874,734;4,924,018; 4,908,463; 4,968,827; 5,329,032; 5,248,801; 5,235,081;5,157,137; 5,103,031; and EP 0 561 476; EP 0 279 586; EP 0 516 476; EP 0594 218; and PCT Publication WO 94/10180.

When the activator is an aluminoxane (modified or unmodified), themaximum amount of activator may be selected to be a 5,000-fold molarexcess over the precursor based on the molar ratio of moles of Al metalatoms in the aluminoxane to moles of metal atoms M (e.g., Zr or Hf) inthe precatalyst (e.g., compound (1)). Alternatively or additionally theminimum amount of activator-to-precatalyst-precursor may be a 1:1 molarratio (Al/M).

Trialkylaluminum compounds may be utilized as activators for precatalyst(e.g., compound (1) or metallocene precatalyst) or as scavengers toremove residual water from polymerization reactor prior to start-upthereof. Examples of suitable alkylaluminum compounds aretrimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, and tri-n-octylaluminum.

The catalyst system may include a support or carrier material. A supportmaterial is a particulate solid that may be nonporous, semi-porous, orporous. A carrier material is a porous support material. Examples ofsupport materials are talc, inorganic oxides, inorganic chloride,zeolites, clays, resins, and mixtures of any two or more thereof.Examples of suitable resins are polystyrene, functionalized orcrosslinked organic supports, such as polystyrene divinyl benzenepolyolefins.

Inorganic oxide support materials include Group 2, 3, 4, 5, 13 or 14metal oxides. The preferred supports include silica, which may or maynot be dehydrated, fumed silica, alumina (see, for example, PCTPublication WO 99/60033), silica-alumina and mixtures thereof. Otheruseful supports include magnesia, titania, zirconia, magnesium chloride(U.S. Pat. No. 5,965,477), montmorillonite (EP 0 511 665),phyllosilicate, zeolites, talc, clays (U.S. Pat. No. 6,034,187), and thelike. Also, combinations of these support materials may be used, forexample, silica-chromium, silica-alumina, silica-titania and the like.Additional support materials may include those porous acrylic polymersdescribed in EP 0 767 184, which is incorporated herein by reference.Other support materials include nanocomposites as disclosed in PCTPublication WO 99/47598; aerogels as disclosed in PCT Publication WO99/48605; spherulites as disclosed in U.S. Pat. No. 5,972,510; andpolymeric beads as disclosed in PCT Publication WO 99/50311.

The support material may have a surface area in the range of from about10 m²/g to about 700 m²/g, a pore volume in the range of from about 0.1cm³/g to about 4.0 cm³/g, and average particle size in the range of fromabout 5 microns to about 500 microns. The support material may be asilica (e.g., fumed silica), alumina, a clay, or talc. The fumed silicamay be hydrophilic (untreated), alternatively hydrophobic (treated). Insome aspects the support is a hydrophobic fumed silica, which may beprepared by treating an untreated fumed silica with a hydrophobing agentsuch as dimethyldichlorosilane, a polydimethylsiloxane fluid, orhexamethyldisilazane. In some aspects the treating agent isdimethyldichlorosilane. In one embodiment, the support is Cabosil™TS-610.

One or more compound(s) (1) and/or one or more activators, andoptionally other precatalyst (e.g., a metallocene or Ziegler-Nattaprecatalyst), may be deposited on, contacted with, vaporized with,bonded to, incorporated within, adsorbed or absorbed in, or on, one ormore support or carrier materials. Such a supported catalyst systemcomprises the inventive catalyst (compound (1) and activator), optionalother catalyst (e.g., metallocene precatalyst or Ziegler-Nattaprecatalyst and activator) is/are in a supported form deposited on,contacted with, or incorporated within, adsorbed or absorbed in, or on,the material.

The compound (1) and/or other precatalysts may be spray dried accordingto the general methods described in U.S. Pat. No. 5,648,310. The supportused with compound (1), and any other precatalysts, may befunctionalized, as generally described in EP 0 802 203, or at least onesubstituent or leaving group is selected as described in U.S. Pat. No.5,688,880.

The metallocene precatalyst may be any one of the metallocene catalystcomponents described in U.S. Pat. No. 7,873,112B2, column 11, line 17,to column 22, line 21. In some aspects the metallocene precatalyst isselected from the metallocene precatalyst species named in U.S. Pat. No.7,873,112B2, column 18, line 51, to column 22, line 5. In some aspectsthe metallocene precatalyst is selected frombis(η⁵-tetramethylcyclopentadienyl)zirconium dichloride;bis(η⁵-tetramethylcyclopentadienyl)zirconium dimethyl;bis(η⁵-pentamethylcyclopentadienyl)zirconium dichloride;bis(η⁵-pentamethylcyclopentadienyl)zirconium dimethyl;(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)(1-methylcyclopentadienyl)zirconiumdimethyl; bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride;bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl;bis(n-propylcyclopentadienyl)hafnium dichloride;bis(n-propylcyclopentadienyl)hafnium dimethyl;bis(n-butylcyclopentadienyl)zirconium dichloride; andbis(n-butylcyclopentadienyl)zirconium dimethyl. In some aspects themetallocene catalyst is a product of an activation reaction of anactivator and any one of the aforementioned metallocene precatalysts.

Polymerization Reactor and Method

Solution phase polymerization and/or slurry phase polymerization ofolefin monomer(s) are well-known. See for example U.S. Pat. No.8,291,115B2.

An aspect of the polymerization method uses a gas-phase polymerization(GPP) reactor, such as a stirred-bed gas phase polymerization reactor(SB-GPP reactor) or a fluidized-bed gas-phase polymerization reactor(FB-GPP reactor), to make the polyolefin polymer. Such reactors andmethods are generally well-known. For example, the FB-GPP reactor/methodmay be as described in U.S. Pat. Nos. 3,709,853; 4,003,712; 4,011,382;4,302,566; 4,543,399; 4,882,400; 5,352,749; 5,541,270; EP-A-0 802 202;and Belgian Patent No. 839,380. These SB-GPP and FB-GPP polymerizationreactors and processes either mechanically agitate or fluidize bycontinuous flow of gaseous monomer and diluent the polymerization mediuminside the reactor, respectively. Other useful reactors/processescontemplated include series or multistage polymerization processes suchas described in U.S. Pat. Nos. 5,627,242; 5,665,818; 5,677,375; EP-A-0794 200; EP-B1-0 649 992; EP-A-0 802 202; and EP-B-634421.

Polymerization operating conditions are any variable or combination ofvariables that may affect a polymerization reaction in the GPP reactoror a composition or property of a bimodal ethylene-co-1-hexene copolymercomposition product made thereby. The variables may include reactordesign and size; compound (1) composition and amount; reactantcomposition and amount; molar ratio of two different reactants; presenceor absence of feed gases such as H₂ and/or O₂, molar ratio of feed gasesversus reactants, absence or concentration of interfering materials(e.g., H₂O), absence or presence of an induced condensing agent (ICA),average polymer residence time in the reactor, partial pressures ofconstituents, feed rates of monomers, reactor bed temperature (e.g.,fluidized bed temperature), nature or sequence of process steps, timeperiods for transitioning between steps. Variables other than that/thosebeing described or changed by the method or use may be kept constant.

In operating the polymerization method, control individual flow rates ofethylene (“C₂”), hydrogen (“H₂”) and 1-hexene (“C₆” or “C_(x)” wherein xis 6) to maintain a fixed comonomer to ethylene monomer gas molar ratio(C_(x)/C₂, e.g., C₆/C₂) equal to a described value (e.g., 0.00560 or0.00703), a constant hydrogen to ethylene gas molar ratio (“H₂/C₂”)equal to a described value (e.g., 0.00229 or 0.00280), and a constantethylene (“C₂”) partial pressure equal to a described value (e.g., 1,000kPa). Measure concentrations of gases by an in-line gas chromatograph tounderstand and maintain composition in the recycle gas stream. Maintaina reacting bed of growing polymer particles in a fluidized state bycontinuously flowing a make-up feed and recycle gas through the reactionzone. Use a superficial gas velocity of 0.49 to 0.67 meter per second(m/sec) (1.6 to 2.2 feet per second (ft/sec)). Operate the FB-GPPreactor at a total pressure of about 2344 to about 2413 kilopascals(kPa) (about 340 to about 350 pounds per square inch-gauge (psig)) andat a described first reactor bed temperature RBT. Maintain the fluidizedbed at a constant height by withdrawing a portion of the bed at a rateequal to the rate of production of particulate form of the bimodalethylene-co-1-hexene copolymer composition, which production rate may befrom 10 to 20 kilograms per hour (kg/hour). Remove the product bimodalethylene-co-1-hexene copolymer composition semi-continuously via aseries of valves into a fixed volume chamber, wherein this removedbimodal ethylene-co-1-hexene copolymer composition is purged to removeentrained hydrocarbons and treated with a stream of humidified nitrogen(N₂) gas to deactivate any trace quantities of residual catalyst. Seepolymerization method described herein.

The catalyst system may be fed into the polymerization reactor(s) in“dry mode” or “wet mode”, alternatively dry mode, alternatively wetmode. The dry mode is a dry powder or granules. The wet mode is asuspension in an inert liquid such as mineral oil.

Induced condensing agent (ICA). An inert liquid useful for coolingmaterials in gas phase polymerization reactor(s). Its use is optional.The ICA may be a (C₅-C₂₀)alkane, e.g., 2-methylbutane (i.e.,isopentane). The methods that use the ICA may be referred to as being aninduced condensing mode operation (ICMO). ICMO is described in U.S. Pat.Nos. 4,453,399; 4,588,790; 4,994,534; 5,352,749; 5,462,999; and6,489,408. Measure concentration of ICA in gas phase using gaschromatography by calibrating peak area percent to mole percent (mol %)with a gas mixture standard of known concentrations of ad rem gas phasecomponents. Concentration of ICA may be from 1 to 10 mol %.

The polymerization conditions may further include one or more additivessuch as a chain transfer agent or a promoter. The chain transfer agentsare well known and may be alkyl metal such as diethyl zinc. Promotersare known such as in U.S. Pat. No. 4,988,783 and may include chloroform,CFCI₃, trichloroethane, and difluorotetrachloroethane. Prior to reactorstart up, a scavenging agent may be used to react with moisture andduring reactor transitions a scavenging agent may be used to react withexcess activator. Scavenging agents may be a trialkylaluminum. Gas phasepolymerizations may be operated free of (not deliberately added)scavenging agents. The polymerization conditions for gas phasepolymerization reactor/method may further include an amount (e.g., 0.5to 200 ppm based on all feeds into reactor) of a static control agentand/or a continuity additive such as aluminum stearate orpolyethyleneimine. The static control agent may be added to the FB-GPPreactor to inhibit formation or buildup of static charge therein.

In an embodiment the method uses a pilot scale fluidized bed gas phasepolymerization reactor (Pilot Reactor) that comprises a reactor vesselcontaining a fluidized bed of a powder of the bimodalethylene-co-1-hexene copolymer composition, and a distributor platedisposed above a bottom head, and defining a bottom gas inlet, andhaving an expanded section, or cyclone system, at the top of the reactorvessel to decrease amount of resin fines that may escape from thefluidized bed. The expanded section defines a gas outlet. The PilotReactor further comprises a compressor blower of sufficient power tocontinuously cycle or loop gas around from out of the gas outlet in theexpanded section in the top of the reactor vessel down to and into thebottom gas inlet of the Pilot Reactor and through the distributor plateand fluidized bed. The Pilot Reactor further comprises a cooling systemto remove heat of polymerization and maintain the fluidized bed at atarget temperature. Compositions of gases such as ethylene, alpha-olefin(e.g., 1-hexene), and hydrogen being fed into the Pilot Reactor aremonitored by an in-line gas chromatograph in the cycle loop in order tomaintain specific concentrations that define and enable control ofpolymer properties. The catalyst system may be fed as a slurry or drypowder into the Pilot Reactor from high pressure devices, wherein theslurry is fed via a syringe pump and the dry powder is fed via a metereddisk. The catalyst system typically enters the fluidized bed in thelower ⅓ of its bed height. The Pilot Reactor further comprises a way ofweighing the fluidized bed and isolation ports (Product DischargeSystem) for discharging the powder of bimodal ethylene-co-1-hexenecopolymer composition from the reactor vessel in response to an increaseof the fluidized bed weight as polymerization reaction proceeds.

In some embodiments the FB-GPP reactor is a commercial scale reactorsuch as a UNIPOL™ reactor or UNIPOL™ II reactor, which are availablefrom Univation Technologies, LLC, a subsidiary of The Dow ChemicalCompany, Midland, Michigan, USA.

In some aspects any compound, composition, formulation, material,mixture, or reaction product herein may be free of any one of thechemical elements selected from the group consisting of: H, Li, Be, B,C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co,Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd,Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg,Tl, Pb, Bi, lanthanoids, and actinoids; with the proviso that chemicalelements required by the compound, composition, formulation, material,mixture, or reaction product (e.g., Zr required by a zirconium compound,or C and H required by a polyethylene, or C, H, and O required by analcohol) are not counted.

Bimodal. Having (only) two maxima in a frequency distribution.

Bimodal in reference to a polymer composition means the polymercomposition consists essentially of a higher molecular weight (HMW)component and a lower molecular weight (LMW) component. Bimodal polymercompositions include post-reactor blends (wherein the LMW and HMWcomponents are synthesized in different reactors or in a same reactor atdifferent times separately and later blended together such as by meltextrusion) and reactor blends (wherein the LMW and HMW components aresynthesized in the same reactor). The bimodal copolymer composition maybe characterized by two peaks separated by a distinguishable localminimum therebetween in a plot of dW/d Log(MW) on the y-axis versusLog(MW) on the x-axis to give a Gel Permeation Chromatograph (GPC)chromatogram, wherein Log(MW) and dW/d Log(MW) are as defined herein andare measured by Gel Permeation Chromatograph (GPC) Test Method describedherein.

Bimodal referring to a catalyst system means a catalyst system thatcontains two different catalysts for catalyzing a same polymerizationprocess (e.g., olefin polymerization) and producing a bimodal polymercomposition. Two catalysts are different if they differ from each otherin at least one of the following characteristics: (a) their catalyticmetals are different (Ti versus Zr, Zr versus Hf, Ti versus Hf; notactivator metals such as Al); (b) one catalyst has a functional ligandcovalently bonded to its catalytic metal and the other catalyst is freeof functional ligands bonded to its catalytic metal; (c) both catalystshave functional ligands covalently bonded to their catalytic metal andthe structures of at least one of functional ligand of one of thecatalysts is different than the structure of each of the functionalligand(s) of the other catalyst (e.g., cyclopentadienyl versuspropylcyclopentadienyl or butylcyclopentadienyl versus(pentamethylphenylamido)ethyl)-amine); and (d) for catalysts disposed ona support material, the compositions of the support materials aredifferent. Functional ligands do not include leaving groups X as definedlater. Two catalysts of a bimodal catalyst system may be disposed on thesame support material, either on the same particles of the same supportmaterial or each on different particles of the same support material.The same catalyst in terms of catalytic metal and ligands wherein aportion thereof is disposed on a support material and a differentportion thereof is dissolved in an inert solvent, the different portionsdo not by themselves constitute a bimodal catalyst system.

Catalyst system. A reaction product of an activation reaction of aprecatalyst and an activator (i.e., a catalyst per se) and, optionally,one or more compatible companion materials such as a different catalystfor making a component of a bimodal polymer, a hydrocarbon solvent forconveying the catalyst, a modifier compound for attenuating reactivityof the catalyst, a support material on which the catalyst is disposed, acarrier material in which the catalyst is disposed, or a combination ofany two or more thereof, or a reaction product of a reaction thereof.

Consisting essentially of, consist(s) essentially of, and the like.Partially-closed ended expressions that exclude anything that wouldaffect the basic and novel characteristics of that which they describe,but otherwise allow anything else. In some aspects any one,alternatively each “comprising” or “comprises” may be replaced by“consisting essentially of” or “consists essentially of”, respectively;alternatively by “consisting of” or “consists of”, respectively.

Consisting of and consists of. Closed ended expressions that excludeanything that is not specifically described by the limitation that itmodifies. In some aspects any one, alternatively each expression“consisting essentially of” or “consists essentially of” may be replacedby the expression “consisting of” or “consists of”, respectively.

Dry. Generally, a moisture content from 0 to less than 5 parts permillion based on total parts by weight. Materials fed to the reactor(s)during a polymerization reaction are dry.

Feed. Quantity of reactant or reagent that is added or “fed” into areactor. In continuous polymerization operation, each feed independentlymay be continuous or intermittent. The quantities or “feeds” may bemeasured, e.g., by metering, to control amounts and relative amounts ofthe various reactants and reagents in the reactor at any given time.

Feed line. A pipe or conduit structure for transporting a feed.

Higher molecular weight (HMW) component. A subgroup of macromoleculeshaving a peak in the GPC plot of dW/d Log(MW) on the y-axis versusLog(MW) on the x-axis that is at a higher molecular weight.

Hydrocarbyl. A monovalent radical formally derived by removing a H atomfrom a hydrocarbon compound consisting of C and H atoms.

Hydrocarbylene. A divalent radical formally derived by removing two Hatoms from a hydrocarbon compound consisting of C and H atoms, whereinthe two H atoms are removed from different carbon atoms of thehydrocarbon compound.

Inert. Generally, not (appreciably) reactive or not (appreciably)interfering therewith in the inventive polymerization reaction. The term“inert” as applied to the purge gas or ethylene feed means a molecularoxygen (O₂) content from 0 to less than 5 parts per million based ontotal parts by weight of the purge gas or ethylene feed.

Lower molecular weight (LMW) component. A subgroup of macromoleculeshaving a peak in the GPC plot of dW/d Log(MW) on the y-axis versusLog(MW) on the x-axis that is at a lower molecular weight.

Metallocene catalyst. Homogeneous or heterogeneous material thatcontains a cyclopentadienyl ligand-metal complex and enhances olefinpolymerization reaction rates. Substantially single site or dual site.Each metal is a transition metal Ti, Zr, or Hf. Each cyclopentadienylligand independently is an unsubstituted cyclopentadienyl group or ahydrocarbyl-substituted cyclopentadienyl group. In some aspects themetallocene catalyst has two cyclopentadienyl ligands, and at least one,alternatively both of the cyclopentenyl ligands independently is ahydrocarbyl-substituted cyclopentadienyl group. Eachhydrocarbyl-substituted cyclopentadienyl group may independently have 1,2, 3, 4, or 5 hydrocarbyl substituents. Each hydrocarbyl substituent mayindependently be a (C₁-C₄)alkyl. Two or more substituents may be bondedtogether to form a divalent substituent, which with carbon atoms of thecyclopentadienyl group may form a ring.

Multimodal. Having two or more maxima in a frequency distribution.

Ziegler-Natta catalysts. Heterogeneous materials that enhance olefinpolymerization reaction rates and are prepared by contacting inorganictitanium compounds, such as titanium halides supported on a magnesiumchloride support, with an activator.

Alternatively precedes a distinct embodiment. ASTM means the standardsorganization, ASTM International, West Conshohocken, Pennsylvania, USA.Any comparative example is used for illustration purposes only and shallnot be prior art. Free of or lacks means a complete absence of;alternatively not detectable. Terms used herein have their IUPACmeanings unless defined otherwise. For example, see Compendium ofChemical Terminology. Gold Book, version 2.3.3, Feb. 24, 2014. IUPAC isInternational Union of Pure and Applied Chemistry (IUPAC Secretariat,Research Triangle Park, North Carolina, USA). Periodic Table of theElements is the IUPAC version of May 1, 2018. May confers a permittedchoice, not an imperative. Operative means functionally capable oreffective. Optional(ly) means is absent (or excluded), alternatively ispresent (or included). Properties may be measured using standard testmethods and conditions. Ranges include endpoints, subranges, and wholeand/or fractional values subsumed therein, except a range of integersdoes not include fractional values. Room temperature: 23° C.±1° C. “HN5”is not pentazole.

EXAMPLES

Isoparaffin fluid: ISOPAR-C from ExxonMobil.

Mineral oil: HYDROBRITE 380 PO White mineral oil from Sonneborn.

Preparation 1A: preparation of an activator formulation comprisingspray-dried methylaluminoxane/treated fumed silica (sdMAO) inhexanes/mineral oil. Slurry 1.6 kg of treated fumed silica (CABOSILTS-610) in 16.8 kg of toluene, then add a 10 wt % solution (11.6 kg) MAOin toluene to give a mixture. Using a spray dryer set at 160° C. andwith an outlet temperature at 70° to 80° C., introduce the mixture intoan atomizing device of the spray dryer to produce droplets of themixture, which are then contacted with a hot nitrogen gas stream toevaporate the liquid from the mixture to give a powder. Separate thepowder from the gas mixture in a cyclone separator, and discharge theseparated powder into a container to give the sdMAO as a fine powder.

Preparation 1B: preparation of a slurry of the activator formulation ofPreparation 1A. Slurry the sdMAO powder of Preparation 1A in a mixtureof 10 wt % n-hexane and 78 wt % mineral oil to give the activatorformulation having 12 wt % sdMAO/treated fumed silica solids in thehexane/mineral oil.

Preparation 2: preparation of a spray-dried metallocene with activatorformulation. Replicate Preparations 1A and 1B except prepare anactivator formulation by slurrying 1.5 kg of treated fumed silica(CABOSIL TS-610) in 16.8 kg of toluene, followed by adding a 10 wt %solution (11.1 kg) of MAO in toluene and(MeCp)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)ZrMe₂, wherein Me ismethyl, Cp is cyclopentadienyl, and MeCp is methylcyclopentadienyl, inan amount sufficient to provide a loading of 40 micromoles Zr per gramof solid. Slurry the resultant powder to give an activator formulationof 22 wt % solids in 10 wt % isoparaffin fluid and 68 wt % mineral oil.Advantageously, the activator formulation does not include a HMWprecatalyst, and can be employed to produce polymer compositions withvery low ratios of HMW/LMW components. Further, transitions to othercatalyst systems are simplified compared to the combining-the-parts feedmethod of the Introduction.

Preparation 3: synthesis of compound (4) {(HN(CH2CH2NHC6(CH3)5)2)}.Replicate Procedure 2 of U.S. Pat. No. 6,967,184B2, column 33, line 53,to column 34, line 9, to give compound (4), as drawn above.

Preparation 4: synthesis of 4-tert-butylbenzylmagnesium chloride. Underan atmosphere of nitrogen in a glovebox having a freezer component,charge a first oven-dried 120 mL glass jar with three small, PTFE-coatedmagnetic stir bars and 1.33 g (54.7 mmol) of magnesium turnings. Sealthe jar with a PTFE-lined cap, and stir contents vigorously for 40hours. PTFE is poly(tetrafluoroethylene). Then add 40 mL anhydrous,degassed diethyl ether. Place the jar in the glovebox freezer for 15minutes to cool the contents of the jar to −30° C. In a secondoven-dried 120 mL glass jar, prepare a solution of4-(1,1,-dimethylethyl)benzyl chloride (2.0 g, 10.9 mmol) in 60 mL ofanhydrous, degassed diethyl ether. Seal the jar with a PTFE-lined cap,and place the second glass jar in the glovebox freezer for 15 minutes tocool its contents to −30° C. Add the solution of the second jar to anaddition funnel, and add dropwise the contents of the addition funnel tothe contents of in the first glass jar over 45 minutes. Use 10 mL ofdiethyl ether to rinse the residual contents of the addition funnel intothe reaction mixture of the first glass jar. Stir the resulting mixtureand allow it to come to room temperature for 2.5 hours. Filter themixture through a PTFE frit into a clean vial to give a solution of4-tert-butylbenzylmagnesium chloride in diethyl ether. Titrate a portionof the filtrate with iodine/LiCl to determine the concentration of the4-tert-butylbenzylmagnesium chloride in the solution.

Preparation 5: synthesis of 3-n-butylbenzyl alcohol. Under an atmosphereof nitrogen in a glove box, charge an oven dried round bottom flask witha PTFE-coated magnetic stir bar and a reflux condenser with3-n-butylbenzoic acid (2.0 g, 11.2 mmol) and 10 mL of dry, degassed THF.Add a solution of borane in tetrahydrofuran (22.4 mL, 22.4 mmol), attacha reflux condenser to the flask, and heat the mixture to reflux for 4hours. Remove the flask from the glove box, and place under anatmosphere of nitrogen on a Schlenk line, then cool to 0° C. in an icebath. Slowly add 5 mL of ethanol, then pour the resulting mixture into30 mL of water, and extract with three 30 mL portions of diethyl ether.Combine and dry the diethyl ether extracts over anhydrous magnesiumsulfate, filter through diatomaceous earth, and concentrate underreduced pressure to give a pale orange oil. Dissolve the oil in aminimal amount of hexane, and pass the solution through a plug of silicaeluting with a 1:1 volume/volume (v/v) mixture of ethyl acetate andhexane. Concentrate the filtrate under reduced pressure to obtain the3-n-butylbenzyl alcohol as a pale orange oil. ¹H NMR (400 MHz,Chloroform-d) δ 7.28-7.23 (m, 1H), 7.19-7.14 (m, 3H), 7.10 (dd, J=7.5,1.5 Hz, 1H), 4.65 (s, 2H), 2.63-2.55 (m, 2H), 1.64 (d, J=11.9 Hz, 2H),1.64-1.54 (m, 2H), 1.41-1.28 (m, 2H), 0.91 (t, J=7.3 Hz, 4H). ¹³C NMR(101 MHz, Chloroform-d) δ 143.31, 140.76, 128.44, 127.77, 127.08,124.26, 65.49, 35.60, 33.63, 22.38, 13.94.

Preparation 6: synthesis of 3-n-butylbenzyl chloride. Under anatmosphere of nitrogen on a Schlenk line, charge a 100 mL round bottomflask with 3-n-butylbenzyl alcohol made in Preparation 5 (1.57 g, 9.6mmol) and add 12 mL of dry degassed dichloromethane. Cool the flask to0° C. in an ice bath, and add 0.1 mL of triethylamine (0.8 mmol) and addthionyl chloride (1.39 mL, 19.1 mmol) slowly via syringe. Stir themixture under an atmosphere of nitrogen and allow to come to roomtemperature over 22 hours. Carefully pour the mixture into 50 mL of icewater and extract with three 30 mL portions of dichloromethane. Wash thecombined dichloromethane layers with two 50 mL portions of saturatedaqueous sodium bicarbonate and two 50 mL portions saturated aqueoussodium chloride, then dry over magnesium sulfate and concentrate underreduced pressure. The 3-n-butylbenzyl chloride is obtained as a paleyellow liquid. ¹H NMR (400 MHz, Chloroform-d) δ 7.25 (dd, J=8.3, 7.4 Hz,1H), 7.21-7.16 (m, 2H), 7.12 (dt, J=7.4, 1.6 Hz, 1H), 4.56 (s, 2H),2.64-2.56 (m, 2H), 1.65-1.50 (m, 3H), 1.34 (dq, J=14.6, 7.3 Hz, 2H),0.92 (t, J=7.3 Hz, 3H). ¹³C NMR (101 MHz, Chloroform-d) δ 143.51,137.32, 128.63, 128.59, 128.51, 125.83, 46.43, 35.50, 33.53, 22.37,13.93.

Preparation 7: synthesis of 3-n-butylbenzylmagnesium chloride. Under anatmosphere of nitrogen in a glovebox having a freezer component, chargea first oven-dried 40 mL glass vial with three small, PTFE-coatedmagnetic stir bars and 330 mg (13.7 mmol) of magnesium turnings. Sealthe vial with a PTFE-lined septum cap, and stir contents vigorously for40 hours. Then add 10 mL anhydrous, degassed diethyl ether. Place thejar in the glovebox freezer for 15 minutes to cool the contents of thejar to −30° C. In a second oven-dried 40 mL glass vial, prepare asolution of 3-(n-butyl)benzyl chloride of Preparation 6 (0.5 g, 10.9mmol) in15 mL of anhydrous, degassed diethyl ether. Seal the jar with aPTFE-lined septum cap, and place the second glass vial in the gloveboxfreezer for 15 minutes to cool its contents to −30° C. Add the solutionof the second jar to an addition funnel, and add dropwise the contentsof the addition funnel to the contents of in the first glass jar over 10minutes. Use 2 mL of diethyl ether to rinse the residual contents of theaddition funnel into the reaction mixture of the first glass jar. Stirthe resulting mixture and allow it to come to room temperature for 1.5hours. Filter the mixture through a PTFE frit into a clean vial to givea solution of 3-n-butylbenzylmagnesium chloride in diethyl ether.Titrate a portion of the filtrate with iodine/LiCl to determine theconcentration of the 3-n-butylbenzylmagnesium chloride in the solution.

Preparation 8: synthesis of tetra(3-methylbenzyl)zirconium. Under anatmosphere of nitrogen in a glovebox having a freezer component, chargea 40 mL oven-dried vial with a PTFE-coated stir bar with zirconium(IV)chloride (0.25 g, 0.6 mmol) and 10 mL of toluene. Seal the vial with aPTFE-lined septum cap and place the vial in the glovebox freezer for 15minutes to cool the contents of the jar to −30° C. Slowly add a solutionof 3-methylbenzylmagnesium chloride (7.35 mL, 2.6 mmol) of Preparation7, then cover the vial with aluminum foil and stir the mixture whileallowing to come to room temperature in the dark for 16 hours. Add 15 mLof diethyl ether and filter the mixture through diatomaceous earth, thenconcentrate the mixture to a volume of about 2 mL. Add a 10 mL portionof pentane place the vial in the glovebox freezer overnight. Collect theresulting yellow precipitate by filtration then triturate the resultingsolid in 5 mL of hexane and dry under vacuum three times to remove theresidual THF. Add 5 mL of toluene to the resulting solid and filterthrough a 0.45 μM PTFE syringe filter. Concentrate the filtrate underreduced pressure, then triturate in 5 mL of hexane and dry under vacuumthree times. Add 5 mL of pentane and place the vial in the glove boxfreezer for 72 hours. Filter the mixture through diatomaceous earth andwash the filter cake with 10 mL of hexane. Concentrate the filtrateunder reduced pressure to give the tetra(3-methylbenzyl)zirconium as ayellow-brown oil. ¹H NMR (400 MHz, Benzene-d₆) δ 7.03 (t, J=7.6 Hz, 1H),6.82 (ddt, J=7.5, 1.8, 0.9 Hz, 1H), 6.34 (dt, J=8.0, 1.4 Hz, 1H), 6.11(d, J=1.9 Hz, 1H), 2.06 (s, 3H), 1.52 (s, 2H). ¹³C NMR (101 MHz,Benzene-d₆) δ 140.90, 140.02, 130.97, 128.68, 125.92, 124.99, 71.42,21.68.

Bimodality Test Method: determine presence or absence of resolvedbimodality by plotting dWf/d Log M (mass detector response) on y-axisversus Log M on the x-axis to obtain a GPC chromatogram curve containinglocal maxima log(MW) values for LMW and HMW polyethylene componentpeaks, and observing the presence or absence of a local minimum betweenthe LMW and HMW polyethylene component peaks. The dWf is change inweight fraction, d Log M is also referred to as d Log (MW) and is changein logarithm of molecular weight, and Log M is also referred to as Log(MW) and is logarithm of molecular weight.

Deconvoluting Test Method: segment the chromatogram obtained using theBimodality Test Method into nine (9) Schulz-Flory molecular weightdistributions. Such deconvolution method is described in U.S. Pat. No.6,534,604. Assign the lowest four MW distributions to the LMWpolyethylene component and the five highest MW distributions to the HMWpolyethylene component. Determine the respective weight percents (wt %)for each of the LMW and HMW polyethylene components in the bimodalethylene-co-1-hexene copolymer composition by using summed values of theweight fractions (Wf) of the LMW and HMW polyethylene components and therespective number average molecular weights (M_(n)) and weight averagemolecular weights (M_(w)) by known mathematical treatment of aggregatedSchulz-Flory MW distributions.

Density is measured according to ASTM D792-13, Standard Test Methods forDensity and Specific Gravity (Relative Density) of Plastics byDisplacement, Method B (for testing solid plastics in liquids other thanwater, e.g., in liquid 2-propanol). Report results in units of grams percubic centimeter (g/cm³).

Gel permeation chromatography (GPC) Test Method: Weight-AverageMolecular Weight Test Method: determine M_(w), number-average molecularweight (M_(n)), and M_(w)/M_(n) using chromatograms obtained on a HighTemperature Gel Permeation Chromatography instrument (HTGPC, PolymerLaboratories). The HTGPC is equipped with transfer lines, a differentialrefractive index detector (DRI), and three Polymer Laboratories PLgel 10μm Mixed-B columns, all contained in an oven maintained at 160° C.Method uses a solvent composed of BHT-treated TCB at nominal flow rateof 1.0 milliliter per minute (mL/min.) and a nominal injection volume of300 microliters (μL). Prepare the solvent by dissolving 6 grams ofbutylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagentgrade 1,2,4-trichlorobenzene (TCB), and filtering the resulting solutionthrough a 0.1 micrometer (μm) PTFE filter to give the solvent. Degas thesolvent with an inline degasser before it enters the HTGPC instrument.Calibrate the columns with a series of monodispersed polystyrene (PS)standards. Separately, prepare known concentrations of test polymerdissolved in solvent by heating known amounts thereof in known volumesof solvent at 160° C. with continuous shaking for 2 hours to givesolutions. (Measure all quantities gravimetrically.) Target solutionconcentrations, c, of test polymer of from 0.5 to 2.0 milligrams polymerper milliliter solution (mg/mL), with lower concentrations, c, beingused for higher molecular weight polymers. Prior to running each sample,purge the DRI detector. Then increase flow rate in the apparatus to 1.0mL/min/, and allow the DRI detector to stabilize for 8 hours beforeinjecting the first sample. Calculate M_(w) and M_(n) using universalcalibration relationships with the column calibrations. Calculate MW ateach elution volume with following equation:

${{\log\mspace{14mu} M_{X}} = {\frac{\log\mspace{14mu}\left( {K_{X}/K_{PS}} \right)}{a_{X} + 1} + {\frac{a_{PS} + 1}{a_{X} + 1}\log\mspace{14mu} M_{PS}}}},$where subscript “X” stands for the test sample, subscript “PS” standsfor PS standards, a_(PS)=0.67, K_(PS)=0.000175, and a_(X) and K_(X) areobtained from published literature. For polyethylenes,a_(X)/K_(X)=0.695/0.000579. For polypropylenesa_(X)/K_(X)=0.705/0.0002288. At each point in the resultingchromatogram, calculate concentration, c, from a baseline-subtracted DRIsignal, I_(DRI), using the following equation: c=K_(DRI)I_(DRI)/(dn/dc),wherein K_(DRI) is a constant determined by calibrating the DRI,/indicates division, and dn/dc is the refractive index increment for thepolymer. For polyethylene, dn/dc=0.109. Calculate mass recovery ofpolymer from the ratio of the integrated area of the chromatogram ofconcentration chromatography over elution volume and the injection masswhich is equal to the pre-determined concentration multiplied byinjection loop volume. Report all molecular weights in grams per mole(g/mol) unless otherwise noted. Further details regarding methods ofdetermining Mw, Mn, MWD are described in US 2006/0173123 page 24-25,paragraphs [0334] to [0341]. Plot of dW/d Log(MW) on the y-axis versusLog(MW) on the x-axis to give a GPC chromatogram, wherein Log(MW) anddW/d Log(MW) are as defined above.

High Load Melt Index (HLMI) I₂₁ Test Method: use ASTM D1238-13, StandardTest Method for Melt Flow Rates of Thermoplastics by ExtrusionPlatometer, 190° C./21.6 kilograms (kg). Report results in units ofgrams eluted per 10 minutes (g/10 min.).

Light-off Test Method: Under an atmosphere of nitrogen in a glovebox,charge a 40 mL glass vial with a PTFE-coated, magnetic stir bar and 0.16g of spray dried methylaluminoxane powder of Preparation 1A. To thecharged vial add 11 mL of 1-octene, and then insert the vial into aninsulated sleeve mounted on a magnetic stir plate turning atapproximately 300 rotations per minute (rpm). To the insulated vial add8 micromoles (μmol) of precatalyst (e.g., compound (1) or HN5Zrdibenzyl). Cap the vial with a rubber septum. Insert a thermocoupleprobe through the rubber septum into the vial such that the tip of thethermocouple probe is below the liquid level. Record the temperature ofthe contents of the vial at 5 second intervals, continuing until afterthe maximum temperature is reached. Download the temperature and timedata to a spreadsheet, and plot thermo-kinetic profiles for analysis.

The Light-off Test Method may be adapted to qualify organometallicprecatalysts and borate activators; assess aging of Ziegler-Natta,molecular catalysts, or pre-polymerized catalysts; characterizeunsupported methylaluminoxanes and methylaluminoxanes chemisorbed onporous silica; assess effects of catalyst poisons; measure activationkinetics of leaving group modifications on organometallic precatalysts;measure effect of reversible coordinating compounds on kinetic profilesof molecular and Ziegler-Natta catalysts; screen activity of newcatalysts, activators, co-catalysts, catalyst modifiers, activatormodifiers, scavengers, chain transfer agents, or chain shuttling agents;assess effects of contaminants in catalysts; characterize Ziegler-Nattacatalysts; and assess olefin monomer purity.

Melt Index I₅ (“I₅”) Test Method: use ASTM D1238-13, using conditions of190° C./5.0 kg. Report results in units of grams eluted per 10 minutes(g/10 min.).

Melt Flow Ratio MFR5: (“I₂₁/I₅”) Test Method: calculated by dividing thevalue from the HLMI I₂₁ Test Method by the value from the Melt Index 15Test Method.

Solubility Test Method: to a 20-mL vial is added, at room temperatureand ambient pressure, a known mass of test precatalyst (e.g., compound(1)) and a known volume of hexanes containing at least 60 weight percentn-hexane. A PTFE-coated magnetic stir bar is added and the mixture isallowed to stir for 1 hour before the vial is removed from the stirplate, and the mixture is allowed to sit overnight. The next day thesuspension is filtered through a 0.4 μm PTFE syringe filter into a taredvial, giving a known mass of supernatant, and the hexanes are removedunder reduced pressure, leaving a measurable mass of the compound offormula (1) from which wt. % solubility is calculated.

Comparative Example 1 (CE1): synthesis of[N′-(2,3,4,5,6-pentamethylphenyl)-N-[2-(2,3,4,5,6-pentamethylphenyl)amino-κN]ethyl]-1,2-ethane-diaminato(2-)κN,κN′]zirconiumdichloride (abbreviated herein as “HN5Zr dichloride”) is described inU.S. Pat. No. 6,967,184B2. Measure the light-off performance accordingto the Light-Off Test Method. Time to maximum temperature result isreported later in Table 1.

Comparative Example 2 (CE2): synthesis ofbis(phenylmethyl)[N′-(2,3,4,5,6-pentamethylphenyl)-N-[2-(2,3,4,5,6-pentamethylphenyl)amino-κN]ethyl]-1,2-ethane-diaminato(2-)κN,κN′]zirconium(abbreviated herein as “HN5Zr dibenzyl”) may be accomplished by reactingHN5Zr dichloride of CE1 with two molar equivalents of benzylmagnesiumchloride in anhydrous tetrahydrofuran. Measure the light-off performanceaccording to the Light-Off Test Method and measure the according to theSolubility Test Method. Solubility and time to maximum temperatureresults are reported later in Table 1.

Inventive Example 1 (IE1): synthesis of compound (3a) (compound (3)wherein each R¹⁰ is methyl) from compound (4), which is preparedaccording to Preparation 3.

Under a nitrogen atmosphere in a glovebox, charge an oven-dried 400 mLglass jar with a PTFE-coated magnetic stir bar, compound (4) (10 g, 25.3mmol), and 200 mL of dry, degassed n-pentane. Then add solidtetrakis(dimethylamino)zirconium(IV) (6.76 g, 25.3 mmol) in smallportions, and stir the resulting mixture at 25° C. for 16 hours. Coolthe mixture in a freezer in the glove-box for 1 hour. Filter offprecipitated (3a), and wash the filtercake with cold n-pentane. Dry thewashed compound (3a) under reduced pressure to give 12.62 g (87.1%yield) of compound (3a) as a white powder. ¹H NMR (400 MHz, Benzene-d₆)δ 3.37 (dt, 2H), 3.10 (d, 6H), 3.02 (dd, 3H), 2.68 (dq, 4H), 2.51 (d,12H), 2.20 (q, 18H), 2.14 (s, 7H), 1.84 (s, 1H); ¹³C NMR (101 MHz,Benzene-d₆) δ 149.77, 132.34, 132.14, 130.04, 129.98, 129.32, 56.29,48.86, 44.35, 40.91, 17.31, 17.27, 16.72, 16.65, 16.09.

Inventive Example 2 (IE2): synthesis of compound (2a) (compound (2)wherein M is Zr and each X is Cl) from compound (3a)

Under a nitrogen atmosphere in a glovebox, charged an oven-dried 400 mLglass jar with a PTFE-coated, magnetic stir bar, compound (3a) (12.62 g,22.0 mmol), and 250 mL of dry, degassed diethyl ether. Addchlorotrimethylsilane (6.2 mL, 48.5 mmol), and stir the mixture at 25°C. for 24 hours. Cool the mixture in the glove box freezer for 1 hour.Filter off precipitated (2a), and wash the filtercake with coldn-pentane. Dry the washed (2a) under reduced pressure to give 10.77 g(88.0% yield) of compound (2a), i.e.,bis(2-(pentamethylphenylamido)ethyl)-amine zirconium(IV) dichloride, asa white powder. ¹H NMR (400 MHz, Benzene-d₆) δ 3.40 (dt, 1H), 2.95 (dt,1H), 2.59 (dp, 2H), 2.49 (s, 3H), 2.46 (s, 3H), 2.43-2.34 (m, 1H), 2.13(s, 3H), 2.06 (s, 3H), 2.04 (s, 3H). ¹³C NMR (101 MHz, Benzene-d₆) δ145.64, 133.37, 133.20, 132.61, 129.84, 129.57, 57.69, 48.97, 17.03,17.01, 16.70, 16.47.

Inventive Example 3 (IE3): synthesis of compound (1A) (compound (1)wherein M is Zr and each R is CH₂-(1,4-phenylene)-C(CH₃)₃) from compound(2a)

Charge a clean oven dried jar with a PTFE-coated magnetic stir bar, thecompound (2a) (1.5 g, 2.69 mmol), and 100 mL of dry, degassed toluene tomake a solution of compound (2a) in toluene. Place the jar in a gloveboxfreezer along with a separate bottle containing the solution of4-tert-butylbenzylmagnesium chloride of Preparation 4 for 15 minutes tocool to −30° C. Then add the solution of 4-tert-butylbenzylmagnesiumchloride to an addition funnel, and add the contents of the additionfunnel dropwise to the solution of the compound (2a). Stir the mixtureand allow it to come to room temperature (r.t.) over 1 hour. Then add0.5 mL of 1,4-dioxane, and filter the resulting mixture throughdiatomaceous earth. Concentrate the filtrate under reduced pressure, andtake up the resulting residue in 30 mL of toluene. Again filter throughand concentrate under reduced pressure to give a twicefiltered/concentrated residue. Triturate the residue with three 10 mLportions of hexane, and dry the triturated residue under reducedpressure to ensure complete removal of toluene. Add 20 mL of pentane tothe residue, and place the resulting mixture in the glovebox freezer for72 hours to give a yellow precipitate, which is collected by filtrationthrough a chilled PTFE frit and dried under reduced pressure to give0.95 g of compound (1A) (45% yield). ¹H NMR (400 MHz, Benzene-d₆) δ7.31-7.23 (m, 2H), 7.18-7.07 (m, 4H), 5.73-5.66 (m, 2H), 3.45 (dt,J=11.8, 5.5 Hz, 2H), 3.25 (dd, J=9.8, 4.5 Hz, 1H), 3.15 (dt, J=12.0, 5.7Hz, 2H), 2.76-2.65 (m, 2H), 2.49 (d, J=4.4 Hz, 13H), 2.28 (s, 6H), 2.14(d, J=18.8 Hz, 11H), 1.77 (s, 2H), 1.33 (s, 8H), 1.21 (s, 8H), 0.87 (s,2H). ¹³C NMR (101 MHz, Benzene-d₆) δ 152.70, 148.52, 147.67, 142.21,136.97, 133.69, 132.32, 131.19, 130.57, 130.41, 129.41, 126.93, 125.50,124.38, 63.41, 58.04, 53.38, 49.37, 34.13, 34.08, 31.90, 31.88, 17.18,17.14, 17.06, 16.68, 16.61. Measure the light-off performance accordingto the Light-Off Test Method and measure the according to the SolubilityTest Method. Solubility and time to maximum temperature results arereported later in Table 1.

Inventive Example 4 (IE4) (prophetic): preparation of solutions ofcompound (1A) (compound (1) wherein M is Zr and each R isCH₂-(1,4-phenylene)-C(CH₃)₃) in hexane. Dissolve measured quantities ofcompound (1A) in separate aliquots of hexane to give 700 mL of 0.91 wt %compound (1A) in hexane, 700 mL of 1.18 wt % compound (1A) in hexane,and 550 mL of 0.91 wt % compound (1A) in hexane, respectively. Thesolutions do not need to be chilled but may be transported or stored at25° C.

Inventive Example 5 (IE5) (prophetic): preparation of a precatalystformulation of compound (1A) in alkanes. Charge the three solutions ofcompound (1A) of IE4 to a 106 liter (L) capacity cylinder. Add 11.3kilograms (kg) of high purity isopentane to the cylinder to give aprecatalyst formulation of 0.10 wt % solution of compound (1A) inhexane/isopentane mixture. The precatalyst formulation of compound (1A)does not need to be chilled, but may be transported or stored at 25° C.

Inventive Example 6 (IE6) (prophetic): making unimodal catalyst systemfrom compound (1A) and activator. Separately feed the activatorformulation of Preparation 1B through a catalyst injection tube and feedfreshly-prepared precatalyst system of IE5 through a different catalystinjection tube into an in-line mixer, wherein the contact each other togive the unimodal catalyst system, which then flows through an injectiontube into the reactor.

Inventive Example 7 (IE7) (prophetic): making a bimodal catalyst systemcomprising a non-metallocene catalyst made from compound (1A) and ametallocene catalyst made from(MeCp)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)ZrMe₂, wherein Me ismethyl, Cp is cyclopentadienyl, and MeCp is methylcyclopentadienyl.Separately feed the spray-dried metallocene with activator formulationof Preparation 2 through a catalyst injection tube and feed theprecatalyst formulation of compound (1A) of IE5 through a differentcatalyst injection tube into an in-line mixer, wherein the feeds contacteach other to form the catalyst system, which then flows through aninjection tube into the reactor.

Inventive Example 8 (IE8) (prophetic): copolymerization of ethylene and1-hexene using a unimodal catalyst system prepared from compound (1A) tomake a unimodal poly(ethylene-co-1-hexene) copolymer. For each run, usea gas phase fluidized bed reactor that has a 0.35 m internal diameterand 2.3 m bed height and a fluidized bed primarily composed of polymergranules. Pass fluidization gas through the bed at a velocity of from0.51 meter per second (m/s) to 0.58 m/s. Exit the fluidization gas fromthe top of the reactor, and pass the exited gas through a recycle gasline having a recycle gas compressor and heat exchanger beforere-entering it into the reactor below a distribution grid. Maintain aconstant fluidized bed temperature of 105° C. by continuously adjustingthe temperature and/or flow rate of cooling water used for temperaturecontrol. Introduce gaseous feed streams of ethylene, nitrogen andhydrogen together with 1-hexene comonomer into the recycle gas line.Operate the reactor at a total pressure of 2410 kilopascals gauge (kPagauge). Vent the reactor to a flare to control the total pressure.Adjust individual flow rates of ethylene, nitrogen, hydrogen and1-hexene to maintain gas composition targets. Set ethylene partialpressure at 1.52 megapascal (MPa). Set the 1-hexene/ethylene (C₆/C₂)molar ratio to 0.0050 and the hydrogen/ethylene (H₂/C₂) molar ratio to0.0020. Maintain ICA (isopentane) concentration at 8.5 to 9.5 mol %.Measure concentrations of all gasses using an on-line gas chromatograph.Feed freshly-prepared unimodal catalyst system of IE6 into thepolymerization reactor at a rate sufficient to maintain a productionrate of about 13 to 16 kg/hour poly(ethylene-co-1-hexene) copolymer,while also controlling feed rate to achieve a loading of 50 micromolesof zirconium per gram of spray dried solids. Thepoly(ethylene-co-1-hexene) copolymer (“resin”) is characterized asunimodal molecular weight distribution, and by a high load melt index(HLMI or I₂₁) in g/10 minutes, a density of in g/cm³, a number-averagemolecular weight (M_(n)), a weight-average molecular weight (M_(w)), az-average molecular weight (M_(z)), and a molecular weight distribution(M_(w)/M_(n)). IE8 makes a unimodal high molecular weight copolymerusing a unimodal catalyst system comprising an activator formulationthat does not comprise a precatalyst, and a precatalyst formulationcomprising precatalyst (1) that does not contain activator. Expectedresin particle size and particle size distribution data are shown laterin Table 2.

Inventive Example 9 (IE9) (prophetic): copolymerization of ethylene and1-hexene using a bimodal catalyst system prepared from compound (1A) anda metallocene to make a bimodal poly(ethylene-co-1-hexene) copolymer.Replicate the polymerization procedure of IE8 except instead of feedingthe unimodal catalyst system of IE6 feed the bimodal catalyst system ofIE7 into the reactor. Adjust the ratio of compound (1A) feed tospray-dried metallocene slurry to adjust the high load melt index (121)of the bimodal poly(ethylene-co-1-hexene) copolymer in the reactor toapproximately 6 g/10 minutes. Increase the C6/C2 molar ratio to 0.0060to reduce the density of bimodal poly(ethylene-co-1-hexene) copolymer.Adjust the feed rate of the spray dried metallocene slurry and compound(1A) solution at a rate sufficient to maintain a production rate ofabout 13 to 16 kg/hour of the bimodal poly(ethylene-co-1-hexene)copolymer. The bimodal poly(ethylene-co-1-hexene) copolymer produced isbimodal, has an 121 of 6 g/10 minutes, a melt flow ratio (121/15), adensity in g/cm³, M_(n), M_(w), M_(z), and M_(w)/M_(n). The bimodalityof the bimodal poly(ethylene-co-1-hexene) copolymer of IE9 isillustrated by the prophetic GPC plot shown in FIG. 1 . Expected resinparticle size and particle size distribution data are given later inTable 2.

Inventive Example 10 (IE10): synthesis of compound (1B) (compound (1)wherein M is Zr and each R is CH₃) from compound (2a).

Under an atmosphere of nitrogen in a glovebox, charge an oven-dried 100mL glass jar with a PTFE-coated magnetic stir bar, compound (2a) (0.5 g,0.9 mmol), and 25 mL of dry, degassed dichloromethane. Place the mixturein the glove box freezer for 1 hour to cool to −30° C. Slowly add a 3.0M solution of methylmagnesium bromide in diethyl ether (0.6 mL, 1.8mmol) with stirring, then allow the mixture to warm to room temperaturewith stirring for 30 minutes. Quench the mixture with 0.2 mL of1,4-dioxane, then filter it through PTFE, and concentrate the filtrateunder reduced pressure. Triturate the residue in 20 mL of n-pentane, andfilter the resulting solid. Dry the solid under reduced pressure to give0.32 g (69% yield) of compound (1B) as a pale orange powder. ¹H NMR (400MHz, Benzene-d₆) δ 3.40 (ddd, J=12.3, 8.9, 5.5 Hz, 3H), 3.11 (ddd,J=12.3, 5.2, 3.3 Hz, 2H), 2.51 (s, 7H), 2.49 (s, 7H), 2.47-2.42 (m, 5H),2.21 (s, 6H), 2.18 (s, 7H), 2.11 (s, 7H), 0.17 (s, 3H), 0.07 (s, 3H).Measure the light-off performance according to the Light-Off Test Methodand measure the according to the Solubility Test Method. Solubility andtime to maximum temperature results are reported later in Table 1.

Inventive Example 11 (IE11): synthesis of compound (1C) (compound (1)wherein M is Zr and each R is CH₂-(1,3-phenylene)-C₄H₉) from compound(2a)

Charge a clean oven dried jar with a PTFE-coated magnetic stir bar withthe compound (2a) (0.4 g, 0.7 mmol), and 20 mL of dry, degassed tolueneto make a solution of compound (2a) in toluene. Place the jar in aglovebox freezer along with a separate bottle containing the solution of3-n-butylbenzylmagnesium chloride of Preparation 7 for 15 minutes tocool to −30° C. Then add the solution of 3-n-butylbenzylmagnesiumchloride to an addition funnel, and add the contents of the additionfunnel dropwise to the solution of the compound (2a). Stir the mixtureand allow it to come to room temperature (r.t.) over 16 hours. Then add20 mL of diethyl ether, and filter the resulting mixture throughdiatomaceous earth. Concentrate the filtrate under reduced pressure, andtake up the resulting residue in 30 mL of toluene. Again filter throughdiatomaceous earth and concentrate under reduced pressure to give atwice filtered/concentrated residue. Triturate the residue with three 10mL portions of hexane, and dry the triturated residue under reducedpressure to ensure complete removal of toluene. Add 20 mL of pentane tothe residue, and place the resulting mixture in the glovebox freezer for72 hours to give a yellow precipitate, which is collected by filtrationthrough a chilled PTFE frit and dried under reduced pressure to give0.12 g of compound (1C) (22% yield). ¹H NMR (400 MHz, Benzene-d₆) δ 7.21(t, J=7.4 Hz, 1H), 7.08-7.01 (m, 2H), 6.88 (t, J=7.5 Hz, 1H), 6.81 (dt,J=7.6, 1.4 Hz, 1H), 6.76-6.71 (m, 1H), 5.58-5.51 (m, 2H), 3.48 (dt,J=11.8, 5.6 Hz, 2H), 3.34 (s, 1H), 3.19 (dt, J=12.1, 5.8 Hz, 2H), 2.73(dq, J=12.2, 6.0 Hz, 3H), 2.61 (td, J=7.5, 6.9, 4.0 Hz, 5H), 2.48 (d,J=5.8 Hz, 10H), 2.27 (s, 6H), 2.15 (s, 7H), 2.11 (s, 7H), 1.83 (s, 2H),1.72-1.61 (m, 3H), 1.44-1.35 (m, 3H), 1.31 (dd, J=14.8, 7.4 Hz, 3H),0.93 (s, 2H), 0.93-0.86 (m, 3H). ¹³C NMR (101 MHz, Benzene-d₆) δ 147.35,146.46, 142.43, 133.37, 132.09, 131.93, 130.96, 130.25, 130.11, 124.83,123.77, 121.68, 119.94, 63.63, 57.68, 53.33, 49.12, 36.11, 36.07, 32.67,22.32, 16.82, 16.78, 16.70, 16.35, 16.29, 13.79. Measure the light-offperformance according to the Light-Off Test Method and measure theaccording to the Solubility Test Method. Solubility and time to maximumtemperature results are reported later in Table 1.

Inventive Example 12 (IE12): synthesis of compound (1D) (compound (1D)wherein M is Zr and each R is CH₂-(1,3-phenylene)-CH₃) from compound (4)

Charge a clean oven dried 40 mL vial with a PTFE-coated magnetic stirbar with tetra(3-methylbenzyl)zirconium of Preparation 8 (0.12 g, 0.2mmol) and 5 mL of dry, degassed toluene. Add the compound 4 as a solidto the vial and stir the mixture at room temperature for 2 hours. Add 30mL of pentane to the mixture and collect a beige solid by filtration,then wash the solid with 10 mL of cold pentane to give 88 mg of thedesired product (53.4% yield). ¹H NMR (400 MHz, Benzene-d₆) δ 7.25-7.10(m, 1H), 7.05-6.98 (m, 2H), 6.86-6.70 (m, 3H), 5.50 (d, J=7.8 Hz, 1H),5.44 (s, 1H), 3.53-3.40 (m, 2H), 3.29-3.20 (m, 1H), 3.15 (dt, J=12.0,5.8 Hz, 2H), 2.69 (q, J=6.1, 5.5 Hz, 3H), 2.57 (td, J=10.9, 5.3 Hz, 2H),2.47 (s, 6H), 2.42 (s, 6H), 2.29 (s, 3H), 2.24 (s, 7H), 2.15 (s, 7H),2.10 (s, 7H), 1.98 (s, 3H), 1.78 (s, 2H), 0.91-0.83 (m, OH), 0.87 (s,2H). ¹³C NMR (101 MHz, Benzene-d₆) δ 147.27, 141.46, 137.28, 133.33,132.11, 131.90, 130.95, 130.22, 130.14, 125.71, 124.35, 121.30, 120.39,63.48, 57.66, 53.13, 49.13, 21.59, 16.77, 16.71, 16.34, 16.27. Measurethe light-off performance according to the Light-Off Test Method andmeasure the according to the Solubility Test Method. Solubility and timeto maximum temperature results are reported later in Table 1.

Comparative Example 3 (CE3): copolymerization of ethylene and 1-hexeneusing a comparative unimodal catalyst system made with HN5Zr dibenzyl ofCE2 in a spray-dried formulation with hydrophobic fumed silica and MAOto make a comparative unimodal poly(ethylene-co-1-hexene) copolymer.Replicate the procedure of IE8 except using the comparative unimodalcatalyst system instead of the unimodal catalyst system of IE6. Thecomparative poly(ethylene-co-1-hexene) copolymer is characterized asunimodal molecular weight distribution, an high load melt index (HLMI orI₂₁) of 0.20 g/10 minutes and a density of 0.9312 g/cm³. Resin particlesize and particle size distribution are shown later in Table 2.

TABLE 1 solubility in hexanes containing at least 60 wt % n-hexane andlight-off performance in polymerization of 1-octene. Solubility inLight-off Performance (Time Precatalyst Hexanes (wt %) to Maximum(minutes) HN5Zr dichloride Not measured 5.2 (CE1) HN5Zr dibenzyl 0.0378.6 (CE2) Compound (1A) 2.3 0.8 Compound (1B) 0.6 1.6 Compound (1C)0.13 8.7 Compound (1D) 0.5 6.3

Compound (1A) has a solubility of 2.3 weight percent in hexanescontaining at least 60 weight percent n-hexane measured according to theSolubility Test Method. Unpredictably, the solubility of compound (1A)in hexanes is 76 times greater than the solubility of HN5Zr dibenzyl(CE2) in hexanes.

Compound (1A) has a time to maximum temperature of 0.8 minute in theLight-Off Test Method. Unpredictably, the time to maximum temperature ofcompound (1A) is 6 times better than HN5Zr dichloride (CE1) and 99 timesbetter than HN5Zr dibenzyl (CE2).

In Table 1, compound (1) has significantly increased solubility inalkanes, which enables reduced complexity of transitions betweencatalyst systems, and has significantly greater light-off performancethan those of comparative precatalyst HN5Zr dibenzyl, which can decreasedistributor plate fouling in gas phase polymerization reactors. Thus,compound (1) solves the aforementioned problems of prior non-MCNprecatalysts.

TABLE 2 resin average particle size and particle size distribution ofCE3 and expected values for IE8 and IE9. CE3 IE8 IE9 Particle Property(measured) (expected) (expected) APS (mm) 0.071 2 1 2.00 mm (10 mesh)screen (wt %) 41.2 60 10 1.00 mm (18 mesh) screen (wt %) 35.5 30 300.500 mm (35 mesh) screen (wt %) 15.3 2 30 0.250 mm (60 mesh) screen (wt%) 6.0 0.2 20 0.125 mm (120 mesh) screen 1.7 0.1 4 (wt %) 0.074 mm (200mesh) screen 0.3 0.1 0.5 (wt %) Bottom Catch Pan (wt %) 0.1 0.00 0.00Fines (wt % of total) 0.4 0.1 0.5

In Table 2, APS (mm) is average particle size in millimeters. Theexpected average particle size of the particles of the propheticinventive unimodal poly(ethylene-co-1-hexene) copolymer of IE8 is largerthan the measured APS of the comparative unimodalpoly(ethylene-co-1-hexene) copolymer of CE3.

The bottom catch pan collects any particles that pass through the 0.074mm (200 mesh) screen. The percent fines is equal to the sum of the wt %of particles that are trapped by the 0.074 mm (200 mesh) screen plus thewt % of particles that pass through the 0.074 mm (200 mesh) screen andare collected in the bottom catch pan. In Table 2, the measured percentfines of the comparative unimodal poly(ethylene-co-1-hexene) copolymerof CE3 is greater than the expected percent fines of the propheticinventive unimodal poly(ethylene-co-1-hexene) copolymer of IE8.

The invention claimed is:
 1. A compound of formula (1):

wherein M is Zr or Hf and each R independently is methyl, anunsubstituted (C₂-C₄)alkyl group, an unsubstituted (C₅-C₁₂)alkyl group,or an unsubstituted or substituted quaternary-arylalkyl group; andwherein at least one R is independently —CH₂QCR¹R²R³; wherein Qindependently is unsubstituted phenylene; wherein each of R¹, R², and R³is independently an unsubstituted (C₁-C₁₅)alkyl.
 2. The compound ofclaim 1 wherein M is Zr.
 3. The compound of claim 1 characterized bysolubility in hexanes containing at least 60 weight percent n-hexane(CH₃(CH₂)₄CH₃) of at least 0.10 weight percent based on total weight ofthe compound and hexanes.
 4. A method of synthesizing the compound offormula (1) of claim 1, the method comprising contacting a compound offormula (2)

wherein M is as defined for compound (1) and each X independently is Cl,Br, or I, with an organometallic reagent of formula X¹MgR or M¹R_(n),wherein R is as defined for compound (1); X¹ is Cl, Br, or I; M¹ is Li,Zn, Sn, or Cu; and subscript n is an integer from 1 to 4 and is equal toa formal oxidation state of M¹, in an aprotic solvent under effectivereaction conditions, thereby synthesizing the compound of formula (1).5. A solution of the compound of claim 1 in an alkane, wherein thesolution is a liquid at 25 degrees Celsius and 101 kilopascals and aconcentration of the compound in the solution is at least 0.10 weightpercent based on weight of the solution.
 6. A catalyst systemcomprising, or a product of an activation reaction of, a compound ofclaim 1, an activator, and optionally a support material.
 7. Thecatalyst system of claim 6 further comprising a metallocene precatalyst,or a product of an activation reaction of the metallocene precatalystand an activator.
 8. A method of making a polyolefin polymer, the methodcomprising contacting the catalyst_system of claim 6, with at least oneolefin monomer that is ethylene, propylene, a (C4-C20)alpha-olefin, or1,3-butadiene in a polymerization reactor under effective polymerizationconditions, thereby making the polyolefin polymer.
 9. A compound offormula (1A):